Liquid hydrocarbon fuels containing high molecular weight mannich bases

ABSTRACT

Reaction products obtained from high molecular weight alkylsubstituted hydroxyaromatic compounds, amines and aldehydes are detergency improvers for liquid hydrocarbon fuels.

United States Patent Otto Mar. 14, 1972 [54] LIQUID HYDROCARBON FUELS2,459,112 1/1949 Oberright ..252/51.5 R CONTAINING HIGH MOLECULAR2,684,293 7/1954 Hill et al. 44/73 X WEIGHT MANNICH BASES 2,962,44211/1960 Andress..... 44/73 X 2,984,550 5/1961 Chamot ..44/73 X [72]Inventor: Ferdinand P. Otto, woodbury, NJ. 3,368,972 2/1968 Otto..252/5l.5 R

3,413,347 11/1968 Worrell ..252/5l.5 R [73] Ass'gnee' Cwpmm 3,416,90312/1968 Eckert et a1. ..44/73 [22] Filed: Dec. 17, 1969 PrimaryExaminerDaniel E. Wyman [21] APPLNO" 885995 AssistantExaminer-W. J.Shine Attorney-Oswald G. Hayes, Andrew L. Gaboriault, Raymond [52] U.S.Cl ..44/73, 252/392 W. Barclay and Claude E. Setliff [51] Int. Cl...Cl011/22 [58] Field of Search ..44/73; 233/392 [57] ABSTRACT Reactionproducts obtained from high molecular weight alkyl- [56] References cuedsubstituted hydroxyaromatic compounds, amines and a1- UNITED STATESPATENTS dehydes are detergency improvers for liquid hydrocarbon fuels.2,348,638 5/1944 Mikeska et a1 ..44/73 X 2,364,502 12/ 1944 Zimmer et al..44/73 X 10 Claims, N0 Drawings LIQUID HYDROCARBON FUELS CONTAININGHIGH MOLECULAR WEIGHT MANNICH BASES BACKGROUND OF THE INVENTION 1. Fieldof the Invention This invention relates to liquid hydrocarbon combustionfuels. More particularly, the invention relates to liquid hydrocarboncombustion fuels having detergency properties imparted thereto byincorporating therein a reaction product of the Mannich base type madeby using a high molecular weight alkyl-substituted hydroxyaromaticcompound.

2. Discussion Of The Prior Art It is well known to those in this artthat liquid hydrocarbon combustion fuels, such as fuel oils andgasolines, tend to exhibit certain deleterious characteristics, eitherafter long periods of storage or under actual operational conditions.Gasolines, for example, in operational use tend to deposit sludge andvarnish at various points in the power system, including carburetor andintake valves. It is desirable, therefore to find a means for improvingliquid hydrocarbon fuels by lessening their tendancy to leave suchdeposits.

US. Pat. No. 3,368,972 discloses the use of Mannich base products inlubricating oils as detergency agents. However, there is no teachingtherein or suggestion therefrom that such products can be used in fuels.

SUMMARY OF THE INVENTION In accordance with this invention, there isprovided a liquid hydrocarbon combustion fuel containing an amountsufficient to impart improved detergency and antirust properties theretoof an additive composition comprising the condensation product of (l ahigh molecular weight alkyl-substituted hydroxy-aromatic compoundwherein said alkyl has a molecular weight of from about 600 to about3,000, (2) an amine, which contains an HN group and (3) an aldehyde,wherein the respective molar ratio of reactants is l:0.l-l:0. 1 -l0.

DESCRIPTION OF SPECIFIC EMBODIMENTS In general aspect, the additivecompositions utilizable in this invention may be made from (I) a highmolecular weight alkyl-substituted phenol, wherein the alkyl substituenthas a molecular weight of from about 600 to about 3,000, preferably fromabout 750 to about 1,200, (2) an aldehyde and (3) an amine whichcontains an I-IN group, i.e'., an active hydrogen, wherein therespective molar ratio of reactants is as already stated.

The reaction involved in preparing the high molecular weight phenol maybe depicted as follows:

(OH) x (OH) x (R)? IR (RI) 1 wherein R is a hydrocarbon or substitutedhydrocarbon radical, R is a polyalkylene compound wherein the repeatingalkyl unit may be from C to C x is an integer from 1 to 2, y is aninteger from 0 to 2 and z is an integer from 1 to 2. Use of this productto form the Mannich bases will become apparent from the Examples setforth hereinafter.

Representative high molecular weight alkyl substituted phenolscontemplated by the present invention are polypropylphenol,polybutylphenol, polyamylphenol and similarly substituted phenols. Forexample, in place of phenol, high molecular weight alkyl substitutedcompounds of resorcinol, hydroquinone, catechol, eresol, xylenol, amylphenol, hydroxydiphenyl, benzylphenol, phenylethylphenol, phenol resins,methylhydroxydiphenyl, guiaeol, alpha and beta naphthol, alpha and betamethylnaphthol, tolylnaphthol, xylylnaphthol, benzylnaphthol, anthranol,phenylmethylnaphthol, phenanthrol, monemethyl ether and catechol,phenoxyphenol, chlorophenol, hydroxyphenyl sulfides and the like may beused.

Aldehydes contemplated by the present invention are the aliphaticaldehydes, typified by formaldehyde (such as trioxymethylene)aeetaldehyde, and aldol (B-hydroxy butyraldehyde); aromatic aldehydes,representative of which is benzaldehyde; heterocyelic aldehydes, such asfurfural; etc. The aldehyde may contain a substituent group such ashydroxyl, halogen, nitro and the like; in short, any substituent whichdoes not take a major part in the reaction. Preference, however, isgiven to the aliphatic aldehydes, formaldehyde being particularlypreferred.

The amines contemplated herein are those which contain an amino groupcharacterized by the presence of at least one active hydrogen atom. Suchamines may contain only primary amino groups, only secondary aminogroups, or both primary and secondary groups. Typical amines are thepolyalkylpolyamines, ethylenediamine, propylenediamine, polyalkenepolyamines (e.g., diethylene triamine, triethylene tetramine); thearomatic amines 0-, mand p-phenylene diamine, diamino naphthalenes; theacid substituted polyalkylpolyamines, N- acctyl tetraethylenepentamine,and the corresponding formylpropionyl-, butyryl-, and the likeN-substituted compounds; and the corresponding eyelized compounds formedtherefrom, such as the N-alkyl amines of imidazolidine and pyrimidine.Secondary heterocyclic amines which are suitable are those characterizedby attachment of a hydrogen atom to a nitrogen atom in the heterocyclicgroup. Representative of the amines contemplated herein are morpholine,thiomorpholine, pyrrole, pyrroline, pyrrolidine, indole, pyrazole,pyrazoline, pyrazolidine, imidazole, imidazoline, imidazolidine,piperidine, phenoxazine, phenthiazine and their substituted analogs.Substituent groups attached to the carbon atoms of these amines aretypified by alkyl, aryl, alkaryl, aralkyl, cycloalkyl, and aminocompounds referred to above.

It is also contemplated that the term amine" shall include the productobtained by reacting an alkenyl succinic anhydride of the formula oralkenyl suecinic acid of the formula with the amines of the foregoingparagraph. See US. Pat. No. 3,346,493.

In the above formulae, R is an alkylene group. The alkenyl radical canbe straight-chain or branched-chain; and it can be saturated at thepoint of unsaturation by the addition of a substance which adds toolefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, oriodine. It is obvious, of course, that there must be at least two carbonatoms in the alkenyl radical, but there is no real upper limit to thenumber of carbon atoms therein, The alkenyl succinic acid anhydrides andthe alkenyl succinic acids are interchangeable for the purposes of thepresent invention. Accordingly, when the term alkenyl suecinic acidanhydride is used herein, it must be clearly understood that it embracesthe alkenyl suceinie acids as well as their anhydrides, and thederivatives thereof in which the olefinic double bond has beensaturated, as set forth hereinbefore. Nonlimiting examples of thealkenyl succinic acid anhydride component are ethenyl succinic acidanhydride; ethenyl suecinie acid; ethyl suceinie acid anhydride;propenyl succinic acid anhydride; sulfurized propenyl succinic acidanhydride; butenyl succinic acid; 2-methylbutenyl suceinic acidanhydride; 1,2-dichloropentyl suceinic acid anhydride; hexenyl succinicacid anhydride; hexyl succinic acid; sulfurized 3-methylpentyl succinicacid anhydride; 2,3-

tiimethylbutenyl succinic acid anhydride; 3.3-dimethylbutenyl iUCCllllCacid; l.2-dibromo-2-ethylbutyl SUCCll'llC acid; heptenyl succmic acidanhydride; l...-diiodooctyl succinic acid; octenyl succinic acidanhydride; diisobutenyl succmic acid anlhydride; .Z-methylheptenylsuccmic acid anhydride; 4-ethylliexenyl succinic acid;l-isopropylphentenyl succmic acid anlnydride; nonenyl succinic acidanhydride'. I-propylhexenyl IiUCClnlC acid anhydride; decenyl succinicacid: decenyl suciainic acid anhydride'. S-methyl-2-isopropyl-hexenylsuccmic .icid anhydride; l.2-dibromo-Z-ethyloctenyl succinic acidanliydride; decyl succinic acid anhydride; undecenyl succinic acidanhydride; 1.2-dichloroundecyl succinic acid; 3-ethyl-2- t-butylpentenylsuccinic acid anhydride: tetrapropenyl suci.:inic acid anhydride'.tetrapropenyl succinic acid; triisobutenyl succinic acid anhydride'.Z-propyl-noneyl succinic acid anliydride; 3-butyloctenyl succinic acidanhydride; tridecenyl :succinic acid anhydride'. tetradecenyl succinicacid anhydride; lhexadecenyl succinic acid anhydride; sulfurizedoctadecenyl iiuccinic acid; octadecyl succinic acid anhydride; l.2-dibromo-Z-meihylpentadecenyl succmic acid anhydride; 8-propylpentadecyl,succinic acid anhydride; eicosenyl succmic acidanhydride; l.2-dichloroZ-methylnonadecenyl succinic acid anhydride;E-octyldodecenyl SUCClDlC acid; [.2- iiliiodotetracosenyl succinic acidanhydride; hexacosenyl suctZlnlC acid; hexacosenyl succmic acidanhydride; and hentriacontenyl succinic acid anhydride. In general.alkenyl suci.:inic acid anhydrides having from about eight to about 35.and preferably. from about nine to about 18 carbon atoms in the alkenylgroup thereof. are most advantageously employed in the novel additivecompositions. Methods for preparing the alkenyl succinic acid anhydridesare well known to those Familiar with the art. the most feasible methodcomprising the reaction of an olefin with maleic acid anhvdride. more.letailed description of the alkenyl succinic acid anhydrides iuitablefor use in the additive compositions of the present iniention and theirpreparation. is disclosed in [1.5. Pat. No. 2.638.450. issued May12..953.

The polyalkyl phenols of this invention may be made by reacting 0.1 tomoles of a phenol with l mole of a polyalkylene in the presence of analkylating catalyst. such as Bl} i including the etherate. phenolate orphosphate complexes), BF or HCl gas. AlCl at 80 to 250 C. This processis particuiarly effective when conducted by reacting l to 1.5. orespecially 1.25 moles. of phenol to l mole of a polyalkylene compound inthe presence of a BF phenolate at about l50 C. The product isconveniently dissolved in an aromatic solvent and then washed with waterto remove unreacted components. Upon filtration and removal of thearomatic solvent bv distilla- H011. the product. a clear. viscous oil.remains.

The preparation of the high molecular weight alkyl-sub- :ititutedphenols used in this invention may be illustrated by the preparation ofpolypropylphenol from phenol and polypropylene with a BF 2C HOH-catalyst. For example. the following was charged into a SO-gallonglass-lined Pfaudler iltettle:

.34 kg. (42.5 moles) polypropylene (M.W.=800) .5 kg. (42.5 moles percentexcess) phenol 13.25 kg. BF 2C H OH 26 percent BF (585 g. BF

The mixture was heated and stirred for 4 hours at 300 F.. then it wascooled down to [75 F. and 14 kg. toluene. 3.4 kg. butyl alcohol and 34kg. distilled water were added to wash but the Bland the unreactedphenol. After that. the mixture in the kettle was washed with 5 percentaqueous KOl-l solution to remove any remaining phenol. then with 5percent aqueous KCL solution to neutralize the unreacted KOH and finallythree times with distilled water until neutral to litmus at atemperature in the vicinity of 150 F.

The washed mixture was filtered through a Sparkler ii-lorizontal platefilter using pound of Hyflo filter aid tdiatomaceous earth) and then thetoluene and butyl alcohol were stripped off under vacuum (-40 mm.) at300 F. The product. a clear. brown. viscous oil. gave the followinganalysis;

active hydrogen (Zerevitinov determination);

lieory nmoles Ch /g. l Hound iilo. 0.85

tield based on the active H analysis= 76.5%.

Ihromatographic clay separation 73.5% yield.

"he high molecular weight alkyl-substituted phenol used in his inventionmay be prepared by any other suitable means.

"The additive composition. i.e.. the aforementioned reaction product. isadded to the fuel in a small amount to attain the objects hereinbeforediscussed. In general. the additive com- TJOSlIlOl'l may vary from about1 to about 200. and. preferably. from about 1 to about 25. pounds perthousand barrels of fuel; )r. in corresponding terms of percent. byweight. the concen tration of additive composition may vary from about0.00025 :0 about 0.l. and preferably. from about 0.00025 to about 3.01percent. by weight. ot'the fuel.

he following examples and comparative data are intended :0 illustratethe novel additive compositions of the present invention and todemonstrate their effectiveness in improving "he properties of liquidhydrocarbon combustion fuels. It will 5e understood. of course. that itis not intended the invention we limited to the particular compositionsshown or to the ioerations or manipulations involved. Various otheradditive compositions. and other fuels. can be utilized. as thoseskilled .n the art will readily appreciate.

EXAMPLE l This example illustrates the Mannich reaction ofpolypropylphenol with dimethylamine and formaldehyde. The "ollowingreactants were employed:

"nlvpropyl henol lM.W 000.

The apparatus consisted of a l-liter. four-necked reaction flaskequipped with a mechanical stirrer. reflux condenser. thermometer.dropping funnel and later. a nitrogen inlet tube.

The polypropylphenol with the mineral oil and .iimethylamine werecharged to the flask at a temperature of 30 C. and the solution offormaldehyde was added dropwise through the dropping funnel withcontinuous stirring. After one hour. the temperature was raised to C.and held there for 3 hours while the dropping funnel was replaced by an.nlet tube and nitrogen gas was passed through. The mixture. afteradding 100 cc. toluene and 50 cc. butyl alcohol. was washed three timeswith hot water until neutral to litmus to remove the unreacted amine andformaldehyde. The solution was filtered and stripped under vacuum (5-10mm.) in a nitrogen atmosphere to 200 C. The product was a clear. orangeoil with the following analysis:

Theory: active hydrogen. 0.41 mmoles CH /g.; oxygen, 0.89%; totalnitrogen. 0.55%; basic nitrogen. 0.55%. Found: active hydrogen. 0.35mmoles CH /g.; oxygen, 0.68%; total nitrogen. 0.45%; basic nitrogen.0.47%.

I EXAMPLE 2 This example illustrates the Mannich reaction ofpolypropylphenol with dimethylaminopropylamine and formaldehyde. Thefollowing reactants were employed:

Polypropylphenol (M.W. 900,

active H'=0.85) 50 g. Mineral oil 50 g. Dimethylaminopropylamine (M.W.I02) l2 g. 37% aqueous formaldehyde 50 g. Xylene l50 cc.

/CH; l CHZO HZNCHZCHgCH N OH A CHzNHCH CHgCHgN H2O The apparatusconsisted of a 500 ml. four-necked reaction flask equipped with amechanical stirrer, reflux condenser, thermometer, dropping funnel andlater, a nitrogen inlet tube.

The polypropylphenol with the mineral oil and dimethylaminopropylaminewere charged to the flask at room temperature and the solution offormaldehyde was added dropwise through the dropping funnel during ahalf hour period with continuous stirring. A cloudy mixture was formed,the temperature rose to 50 C. and 150 cc. xylene was added while thedropping funnel was replaced by an inlet tube and nitrogen gas waspassed through. The mixture was refluxed for 3 hours and after coolingdown was washed with hot water to remove the unreacted amine untilneutral to litmus. Then the xylene was stripped off under vacuum (5-10mm.) at 200 C. The product, a clear, light brown oil gave the followinganalysis:

Theory: total nitrogen, 1.08%; basic nitrogen, 1.08%. Found: totalnitrogen, 0.91%; basic nitrogen, 0.89%.

EXAMPLE 3 This example illustrates the Mannich reaction ofpolypropylphenol with tetraethylenepentamine and paraformaldehyde (ratio2:1:2). The following reactants were employed:

Poiypropylphenol (M.W. 900,

act. H'=0.85) 2,200 g. Tetraethylenepentamine 187 g. Pural'ormaldehyde59.4 g.

The apparatus consisted of a 5-liter, four-necked reaction flaskequipped with a mechanical stirrer, reflux condenser with a Dean-Starkwater takeoff, thermometer, dropping funnel and later, a nitrogen inlettube.

The polypropylphenol and paraformaldehyde were charged to the flask at atemperature of 70 C. and the tetraethylenepentamine was added dropwisethrough the dropping funnel with stirring. The reaction mixture wasstirred and heated to C. in the presence of nitrogen and held at thistemperature for 4 hours. During this time, 34 cc. water was evolved(theory 36 cc.). The product was filtered hot by suction through anelectrically heated Buchner funnel containing a layer of Hyflo clay (adiatomaceous clay filter aid).

The filtrate was a clear, brown, viscous oil with the followinganalysis:

Percent theory: total nitrogen, 2.86; basic nitrogen, 2.86. Percentfound: total nitrogen, 2.61; basic nitrogen, 2.31.

EXAMPLE 4 This example illustrates the Mannich reaction ofpolybutylphenol with tetraethylenepentamine and paraformaldehyde (ratio2: l :2). The following reactants were employed:

Tetraethylenepentamine 15 g. Paral'ormaldehyde 5 g. Polybutylphenol(M.W.= i000) 200 g.

The same procedure was followed as in Example 3. The final product was aclear, brown, viscous oil with the following analysis:

Percent theory: total nitrogen, 2.50; basic nitrogen, 2.50. Percentfound: total nitrogen, 2.42; basic nitrogen, 1.90.

EXAMPLE 5 This example illustrates the Mannich reaction ofpolypropylphenol with N-acetyl-tetraethylenepentamine andparaforrnaldehyde (ratio 2:1:2). The following reactants were employed:

Polypropylphenol (M.W. 900,

act. H=0.85) 2,000 g. N-acetyl-tetraethylenepentamine 196 g.Paraformaldehyde 50 g,

The apparatus consisted of a 5-liter, four-necked reaction flaskequipped with a mechanical stirrer, reflux condenser with a Dean-Starkwater takeoff, thermometer and later, a nitrogen inlet tube.

The polypropylphenol and N-acetyl-tetraethylenepentamine were charged tothe flask at a temperature of 60 C. and the paraformaldehyde was addedslowly in a period of A hour. The reaction mixture was heated andstirred in the presence of nitrogen to 200 C. and held at thistemperature for 4 hours. During this time, 30 cc. water was evolved(theory 30 cc.). The product was filtered hot by suction through anelectrically heated Buchner funnel containing a layer of Hyflo clay, anda clear, brown viscous oil was obtained with the following analysis:

Percent theory: total nitrogen, 2.30; basic nitrogen, 1.84. Percentfound: total nitrogen, 2,43; basic nitrogen, 1.70.

EXAMPLE6 This example illustrates the Mannich reaction ofpolypropylphenol with diethylenetriamine and paraformaldehyde (ratio110.75: 1 The following reactants were employed:

Polypropylphenol (M.W. 900,

act. H=0.85) 2,200 g. Diethylenetriamine 144.43 g. Paraformaldehyde 55g.

The apparatus consisted of a -liter. four-necked reaction flask equippedwith a mechanical stirrer. thermometer. reflux condenser and later aDean-Stark water takeoff was added to the condenser. Thepolypropylphenol and diethylenetriamine were charged to the flask at atemperature of 60 C. and the paraformaldehyde was added slowly over aperiod of 50 minutes. The reaction mixture was stirred and heated to 120C. and held there for 2 hours. At this point. a Dean-Stark water takeoffwas added. nitrogen gas was introduced and the temperature raised to 150C. and held there for 2 /2 hours. During this time. 30 cc. water wasevolved (theory 30 cc.). The mixture was stripped under vacuum (5-10mm.) for 1 hour at 150 C. and 50 g. unreacted amine was recovered. Theproduct was a clear. brown viscous oil which gave the followunganalysis:

Percent theory: total nitrogen, 1.62; basic nitrogen. 1.62.

Percent found: total nitrogen. 1.65; basic nitrogen. 1.60.

EXAMPLE? This example illustrates the Mannich reaction ofpolypropylphenol sulfide with diethylenetriamine and paraformaldehyde.The following reactants were employed:

Polypropylphcnol sulfide (50% Promor The apparatus was the same as inExample 6. The polypropylphenol sulfide mixture (50% Promor No. 5) anddiethylenetriamine were charged to the flask at room temperature and theparaformaldehyde was added slowly over a period of minutes. The reactionmixture was stirred and heated to 180 C. for 3% hours. The mixture inthe flask was stripped under vacuum (5-l0mm.) at I80 C. and someunreacted amine was recovered. The product. a dark brown oil gave thefollowing analysis:

Percent theory: Total nitrogen, 0.77

Percent found: Total nitrogen, 0.69

EXAMPLE 8 The example illustrates the Mannich reaction of wax phenol,where the wax has an average of about 24 carbon atoms, withdiethylenetrlamlneand para formaldehyde (ratio :0.75:1 The followingreactants were employed:

.1-14) Wax phenol Z6l g. liethyleneinamine (M.W 103) 25.5 g."maformuldehyde (MAN 10) 10 g. romor Oil No. 5 (for 509; all dilution)290 g.

The setup consisted of a 2-liter, four-necked reaction flask with amechanical stirrer, thermometer and condenser The wax-phenol, Promor OilNo. 5 and diethylenetriamine were charged to the flask at a temperatureof about 50 C., and the paraformaldehyde was added slowly in a period of1 hour. The reaction mixture was refluxed for 1 hour. Nitrogen gas wasintroduced and the water was removed at a temperature of l30-l50 C. in aperiod of 1V2 hours. Then vacuum was applied (10 mm. Hg) for 1% hours at150 C. After filtratron, a brown oil was obtained which had thefollowing analyits:

Percent found: Total nitrogen, 1.82.

EXAMPLE 9 This example illustrates the Mannich reaction of,polypropylphenol with diethylenetriamine and paraformaldehyde (ratiol:0.6:2). The following reactants were em- :Jloyed:

olvpropylphenol (M.W. 825.

lct. Hfll75) 4000 g. Jiethylenetriamine (M.W. 103) 185 g.Paral'ormaldehyde 180 g. romor Oil No. S (for 25 1' oil dilution) i433g.

The setup consisted ofa l2-liter, four-necked reaction flask equippedwith a mechanical stirrer, condenser, thermometer mo a nitrogen inlettube.

The mixture of polypropylphenol, diethylenetriamine and Promor Oil No. 5were charged in the flask and paraformaldehyde was added slowly in aperiod of 3 hours at a temperature of 70-90 C. The mixture was refluxedfor 2 hours and :he water was removed with nitrogen gas at a temperatureof 00-l50 C. in 1 hour. Then vacuum was applied (5 mm. Hg) r'or 2 hoursat 150 C. and a clear, brown viscous oil was obamed containing 25 oilwhich gave the following analysis:

Percent theory: total nitrogen, [.30. Percent found: total nitrogen,1.30.

EXAMPLE l0 This example illustrates the preparation of monosuccinimideof dodecenyl-succinic anhydride with diethylenetriamine. The followingreactants were employed:

.Jodecenyl-succmic anhydride (2 moles) MW. 266) 533 g.Diethylenetriamine (2 moles +10% excess) M.W. 103) 227 llylene 400 g.

The setup consisted ofa 3-liter, four-necked reaction flask equippedwith a mechanical stirrer, reflux condenser with a Dean-Stark watertakeoff, thermometer, dropping funnel and later a nitrogen inlet tube.

The diethylenetriamine and xylene were charged into the flask anddodecenyl-succinic anhydride was added dropwise in 2 hours at atemperature from 50 C. up to C. Water was removed by refluxing withnitrogen gas for 1% hours at C. (about 55 cc.) and then the mixture wasstripped under vacuum (5 mm. Hg) for 1% hours at 150 C. to remove theunreacted amine. A clear, very viscous product was obtained with thefollowing analysis:

Percent theory: total nitrogen, 11.5. Percent found: total nitrogen,10.56.

EXAMPLE 1 1 This example illustrates the Mannich reaction of (ratio 1:11.5). The following reactants were employed:

Polypropylphenol (active H=0.8) 1500 g.Dodecenybsuccinimitle-diethylenetriamine (Ex. 462 g. Paral'ormaldehyde54 g. Promor Oil No.5 ((012257: oil dilution) 660 g..

The setup consisted of a 5 -lit efifour-necked flask with a mechanicalstirrer, thermometer, nitrogen inlet tube and condenser.

The polypropylphenol, dodecenyl-succinimide and Promor Oil No. 5 werecharged in the flask and paraformaldehyde was added slowly in a periodof 2% hours at a temperature of 8090 C., then the water was removed withnitrogen gas at first under light vacuum and then the mixture wasstripped under 5-10 mm. Hg. vacuum for 3 hours at 150 C. A total of 23cc. water was removed (theory 22 cc. water). The final product was aclear, viscous oil containing 25% Promor No. 5which gave the followinganalysis:

Percent theory: nitrogen, 1.85. Percent found: nitrogen, 1.77.

EXAMPLE 12 This example illustrates the Mannich reaction ofpolypropylphenol with diethylenetriamine and paraformaldehyde (ratio1:0.612) (similar to Example 9 but higher molecular weightpolypropylphenol was used). The following reactants were employed:

Polypropylphenol (polypropylene M.W.

I120. active H=0.76) 2000 g. Diethylenetriamine (M.W. 103) 93.8 g.Parat'ormaldehyde 91.8 g. Promor Oil No. 5 (for 2571 oil dilution) 712.0g.

Percent found: total nitrogen, l .49.

The additive compositions of the present invention impart valuableproperties, as hereinbefore indicated, to liquid hydrocarbon combustionfuels, including the distillate fuels, i.e., gasolines and fuel oils.Accordingly, the fuel oils that may be improved in accordance with thepresent invention are hydrocarbon fractions having an initial boilingpoint of at least about 100 F. and an end-boiling point no higher thanabout 750 F., and boiling substantially continuously throughout theirdistillation range. Such fuel oils are generally known as distillatefuel oils. It is to be understood, however, that this term is notrestricted to straight run distillate fractions. The distillate fueloils can be straight run distillate fuel oils, catalytically orthermally cracked (including hydrocracked) distillate fuel oils, ormixtures of straight run distillate fuel oils, naphthas and the like,with cracked distillate stocks. Moreover, such fuel oils can be treatedin accordance with well-known commercial methods, such as, acid orcaustic treatment, hydrogenation, solvent refining, clay treatment, etc.

The distillate fuel oils are characterized by their relatively lowviscosities, pour points, and the like. The principal property whichcharacterizes the contemplated hydrocarbons, however, is thedistillation range. As mentioned hereinbefore, this range will liebetween about 100 F. and about 750 F. Obviously, the distillation rangeof each individual fuel oil will cover a narrower boiling range falling,nevertheless, within the above-specified limits. Likewise, each fuel oilwill boil substantially continuously throughout its distillation range.

Contemplated among the fuel oils are Nos. 1, 2, and 3 fuel oils used inheating and as diesel fuel oils, and the jet combustion fuels. Thedomestic fuel oils generally conform to the specifications set forth inA.S.T.M. Specifications D396-48T. Specifications for diesel fuels aredefined in A.S.T.M. Specification D975-48T. Typical jet fuels aredefined in Military Specification MlL-F-5624B.

The gasolines that are improved by the additive compositions of thisinvention, are mixtures of hydrocarbons having an initial boiling pointfalling between about F. and about F. and an end-boiling point fallingbetween about 250 F. and about 450 F. As is well known in the art, motorgasoline can be straight run gasoline or, as is more usual, it can be ablend of two or more cuts of materials including straight run stock,catalytic or thermal reformate, cracked stock, alkylated naturalgasoline, and aromatic hydrocarbons. 7

The utility of the Mannich products of this invention as additives forfuels has been shown by a number of comparative tests conducted on thefuel alone and on the fuel blended with minor amounts of the Mannichproducts described in the preceding examples. Both bench tests andengine tests were employed. Carburetor Detergency Test Thedeposit-forming tendencies of a fuel are determined in an 8-hour enginetest. This accelerated test, when run on fuels that contain nodetergents, produces an amount of deposit equivalent to the amountobserved in 4,000 miles of operation in field tests on taxicab fleets. Asix-cylinder Chevrolet engine is equipped with notched rings to increasethe amount of flowby and with a glass throttle body section. The engineis operated for 8 hours, using the fuel under test, at alternate idlingand running cycles. In the idle cycle, the engine is run at idling speedof 400 rpm. with no load, for 5 minutes. Then for 1 minute, the engineis run at a speed of 2,500 rpm. under a load of 30 BPI-I and at 9.4 in.of mercury manifold pressure. During the running cycle, the blowby andpart of the exhaust are released into the carburetor air intake duringthe idling cycle. After 8 hours operation at alternate run and idle, thecarburetor is examined and rated as to the amount of deposit in thethrottle throat. In the rating scale, a rating of 0 (zero) indicates aclean carburetor; l--trace deposits; 2=light deposits; 3=mediumdeposits; and 4=heavy deposits.

CARBURETOR DETERGENCY TEST IN GASOLINE [Inhibitors blended in a fuelcomprising 40% TCC gasoline, 40% reformate and 20% light alkylateapproximately 85-415 F.

boiling range. 3 cc./gallon offuel of tetraethyllead is present] thesecontain same nitrogen content ditto Rust Test In Gasoline The rustingcharacteristics of gasoline were determined in a Static Rust Test, whichsimulates conditions encountered in storage vessels. The gasoline usedwas the same as that used in the Carburetor Detergency Test. The testused was ASTM D- 665 except that the temperature was 80 F. instead of F.and the time was 48 hours instead of 24 hours.

The results of this test were as follows.

MODIFIED ASTM RUST TEST D-665 The unhibited gasoline had a rating of 80%rusting in both specimens.

While the present invention has been described with illustrativeembodiments. it should be understood that modificalions and variationsmay be resorted to without departing from the spirit and scope of theinvention as will be understood by those skilled in this art.

lclaim:

l. A liquid hydrocarbon combustion fuel containing an amount sufficientto impart improved detergency properties thereto of an additivecomposition comprising the condensation product of l a high molecularweight sulfur free alkylsubstituted hydroxyaromatic compound wherein thealkyl has ti molecular weight of from about 600 to about 3.000. (2) anamine which contains an amino group having at least one active hydrogenatom and (3) an aldehyde wherein the respective molar ratio of reactantsis 1:0. ll0:0.1 -10.

2. The liquid hydrocarbon combustion fuel of claim 1 wherein the saidcondensation product comprises from 1 to about 200 pounds per thousandbarrels offuel.

i. The liquid hydrocarbon combustion fuel of claim 1 will) iii lib

wherein the said condensatidrfiart iFct comprises from 1 to mom 25pounds per thousand barrels of fuel.

ll, The liquid hydrocarbon combustion fuel of claim 1 wherein themolecular weight of the alkyl substituent is from about 750 to about[200.

5. The liquid hydrocarbon combustion fuel of claim 1 vnerein thealkyl-substituted hydroxyaromatic compound is in alkyl-substitutedphenol.

ti. The liquid hydrocarbon combustion fuel of claim 1 wherein saidaldehyde is selected from the group consisting of T'ormaldehyde andparaformaldehyde.

l. The liquid hydrocarbon combustion fuel of claim 1 wherein said amineis selected from the group consisting of polyalkylpolyamines.polyalkenylpolyamines, aromatic amines carboxylic acid-substitutedpolyalkylpolyamines, and the succinimide formed from any one of thesewith an olefinic iuccinic acid or anhydride.

8. The liquid hydrocarbon combustion fuel of claim 1 wherein said amineis selected from the group consisting of iiimethylamine.dimethylaminopropylamine, tetraethylenepentamine,N-acetyl-tetraethylenepentamine, diethylenetriamine and themonosuccinimide prepared from clodecenyl succinic anhydride anddiethylenetriamine.

9. The liquid hydrocarbon combustion fuel of claim 1 wherein saidalkyl-substituted hydroxyaromatic compound is selected from the groupconsisting of polypropyl phenol and polybutyl phenol.

10. The liquid hydrocarbon combustion fuel of claim I wherein saidalkyl-substituted hydroxyaromatic compound is polypropyl phenol frompolypropylene having a molecular weight of 825, said amine isdiethylenetriamine, and said aldehyde is paraformaldehyde and the saidrespective molar Notice of Adverse Decision in Interference 0 Patent No.3,6L9,229, F. P. Otto,

In Interference No. 98,623 invoivin LIQUID HYDROCARBON FUELS CONTAININGHIGH MOLECU- LAR \VEIGHT MANNICH BASES, final judgment adverse to thepatentee Oct. 6, 1975, as to claims 1, 2, 3, 4:, 5, 6, 7, 8 and 9.

was rendered [Ofi'im'al Gazette Febmm'y 10, 1976.]

2. The liquid hydrocarbon combustion fuel of claim 1 wherein the saidcondensation product comprises from 1 to about 200 pounds per thousandbarrels of fuel.
 3. The liquid hydrocarbon combustion fuel of claim 1wherein the said condensation product comprises from 1 to about 25pounds per thousand barrels of fuel.
 4. The liquid hydrocarboncombustion fuel of claim 1 wherein the molecular weight of the alkylsubstituent is from about 750 to about 1,200.
 5. The liquid hydrocarboncombustion fuel of claim 1 wherein the alkyl-substituted hydroxyaromaticcompound is an alkyl-substituted phenol.
 6. The liquid hydrocarboncombustion fuel of claim 1 wherein said aldehyde is selected from thegroup consisting of formaldehyde and paraformaldehyde.
 7. The liquidhydrocarbon combustion fuel of claim 1 wherein said amine is selectedfrom the group consisting of polyalkylpolyamines, polyalkenylpolyamines,aromatic amines, carboxylic acid-substituted polyalkylpolyamines, andthe succinimide formed from any one of these with an olefinic succinicacid or anhydride.
 8. The liquid hydrocarbon combustion fuel of claim 1wherein said amine is selected from the group consisting ofdimethylamine, dimethylaminopropylamine, tetraethylenepentamine,N-acetyl-tetraethylenepentamine, diethylenetriamine and themonosuccinimide prepared from dodecenyl succinic anhydride anddiethylenetriamine.
 9. The liquid hydrocarbon combustion fuel of claim 1wherein said alkyl-substituted hydroxyaromatic compound is selected fromthe group consisting of polypropyl phenol and polybutyl phenol.
 10. Theliquid hydrocarbon combustion fuel of claim 1 wherein saidalkyl-substituted hydroxyaromatic compound is polypropyl phenol frompolypropylene having a molecular weight of 825, said amine isdiethylenetriamine, and said aldehyde is paraformaldehyde, and the saidrespective molar ratio is 1:0.6:2.